Substituted phenoxypropionates and herbicidal compositions

ABSTRACT

Novel substituted phenoxypropionate of the formula ##STR1## in which R 1  and R 2  each independently are a hydrogen atom or a C 1  to C 6  alkyl group, 
     X is a hydrogen or halogen atom or a nitro, C 1  to C 6  alkyl or C 1  to C 6  alkoxy group, 
     a and n each independently are 1 or 2, and 
     Ar is a group of the formula ##STR2## wherein Y is a trifluoromethyl group, a halogen atom or a nitro, cyano or C 1  to C 6  alkyl group, and 
     b is 1, 2 or 3, 
     and their use as herbicides. Novel intermediates are taught, of the formula ##STR3## in which Z 1  is halogen or a 4-hydroxyphenoxy group.

This is a division of application Ser. No. 389,525, filed June 17, 1982now U.S. Pat. No. 4,441,913.

The present invention relates to certain novel substitutedphenoxypropionates, to herbicidal compositions containing them and tomethods of combating weeds utilizing such compounds.

The present invention also relates to novel intermediates for thepreparation of said substituted phenoxypropionates.

It has been disclosed in U.S. Pat. No. 4,046,553 corresponding toJapanese Laid-open Patent Application No. 51-106,735 that herbicidalactivity is possessed by compounds of the general formula ##STR4##wherein X¹ and X² each represents halogen,

Y represents hydrogen or alkyl having 6 or less carbon atoms, and

Z represents oxygen or sulfur, and the salts, esters, amides, andhalides thereof.

It has been disclosed in Japanese Laid-open Patent Application No.52-131,545 corresponding to DE-OS (German published specification) No.2,617,804 that herbicidal activity is possessed by compounds of thegeneral formula ##STR5## wherein R represents hydrogen or halogen,

R₁ represents:

(a) straight- or branched chain (C₁ -C₁₂) alkyl (which is substituted bycyclohexyl, halophenyl, nitrophenyl, (C₁ -C₆) alkylphenyl, phenoxy(which is mono- or trisubstituted in some cases with halogen and/or (C₁-C₄) alkyl), (C₅ -C₆) alkoxy, (C₅ -C₆)-alkoxy-(C₂ -C₄) alkoxy, (C₁ -C₄)alkoxyethoxyethoxy, (C₁ -C₄) acyl, a group represented by the generalformula ##STR6## or, in the 2 position or a position remote from thecarboxyl, mono- or poly-substituted by phenyl);

(b) cyclohexenyl or phenyl-(C₃ -C₄)alkenyl;

(c) (C₃ -C₄)alkynyl (which is optionally mono- or disubstituted bystraight or branched chain (C₁ -C₄)alkyl, halogen, phenyl, halophenyl or(C₁ -C₄)alkylphenyl), provided that R₁ does not represent unsubstitutedpropargyl or butynyl;

(d) one of the groups represented by the following general formulae:##STR7## or (e) (C₁ -C₂)alkyl substituted by furyl, tetrahydrofuryl,pyridyl or oxiranyl,

R₂ represents hydrogen, (C₁ -C₄)alkyl or (C₁ -C₄)alkoxy,

R₃ represents hydrogen, (C₁ -C₄)alkyl or phenyl, or

R₂ and R₃ together form 4- or 5-membered, saturated or unsaturatedalkylene chain one methylene of which may optionally be replaced by--O--, ##STR8## or --N--(C₁ -C₄)--alkyl, R₄ represents hydrogen or (C₁-C₄)alkyl,

Z represents an inorganic or organic anion,

R₁ ' represents straight or branched chain (C₁ -C₁₂)alkylene,

R₅ represents hydrogen, (C₁ -C₄)alkyl, (C₁ -C₄)haloalkyl, phenyloptionally substituted by halogen, nitro and/or (C₁ -C₄)alkyl, or grouprepresented by the formula ##STR9## R₆ represents (C₁ -C₄)alkyl, and nis 0, 1 or 2.

It has been disclosed in Japanese Laid-open Patent Application No.52-144,637 corresponding to DE-OS (German published specification) No.2,623,558 that herbicidal activity is possessed by compounds of thegeneral formula ##STR10## wherein each R represents the same ordifferent group selected from halogen, (C₁ -C₄)alkyl, and (C₁-C₄)alkoxy,

Y represents O or S,

n is 1 or 2,

R₁ represents:

(a) straight or branched chain (C₁ -C₁₂)alkyl (which is substituted bycyclohexyl, halophenyl, nitrophenyl, (C₁ -C₄) alkylphenyl, or a grouprepresented by the general formula ##STR11## or mono- orpoly-substituted by the same or different group selected from hydroxy,halogen, rhodanide, and phenyl, in 2- or more distant position from (Y);

(b) mono- or di-(C₁ -C₄)alkylcyclohexyl;

(c) cyclohexenyl or (C₃ -C₄)alkenyl (which may be substituted byhalogen, hydroxy, phenyl, halophenyl or (C₁ -C₄)alkylphenyl);

(d) naphthyl or phenyl (which is in some cases mono- or poly-substitutedby (C₁ -C₄)alkyl, (C₁ -C₃)haloalkyl, CF₃, NO₂, CN, SCN, CHO, (C₁-C₃)alkoxy, (C₁ -C₃)alkoxycarbonyl, aminocarbonyl, di-(C₁-C₄)alkylamino, or (C₁ -C₂)alkylthio, and which may further containhalogen), or when Y is O, R₁ also represents:

(e) straight or branched chain (C₃ -C₆)alkynyl (which is in some casesmono- or poly-substituted by (C₁ -C₄)alkyl, (C₁ -C₄)alkoxy, halogen,phenyl, halophenyl, or (C₁ -C₄) alkylphenyl);

(f) halocyclohexyl optionally substituted by (C₁ -C₄)alkyl;

(g) group represented by the formula of ##STR12## (h) (C₁ -C₂)alkylsubstituted by a furyl, tetrahydrofuryl, pyridyl or by oxiranyl;

(i) (C₂ -C₄)alkyl substituted by 3 to 7 chlorine and/or fluorine, or,when Y is S, R₁ represents:

(k) (C₃ -C₄)alkenyl,

R₂ represents hydrogen, (C₁ -C₄)alkyl, (C₁ -C₄) alkoxy, hydroxyethyl orchloroethyl,

R₃ represents hydrogen, (C₁ -C₄)alkyl, chloroethyl, phenyl, halophenyl,(C₁ -C₄)alkylphenyl, hydroxyethyl or aliphatic (C₁ -C₄)acyl, or, whentaken together,

R₂ and R₃ represents 2-, 4- or 5-membered, saturated or unsaturatedhydrocarbon chain one, carbon atom of which may be replaced by --O--,--CO--, --N--, --NH-- or --N--(C₁ -C₄)alkyl,

R₄ represents hydrogen or (C₁ -C₄)alkyl,

Z represents an inorganic or organic acid anion,

R₁ ' represents a straight chain or branched chain (C₁ -C₁₂)alkylene,

R₅ represents (C₁ -C₆)alkyl, (C₁ -C₄)haloalkyl, (C₂ -C₈)alkoxyalkyl, (C₃-C₁₂)alkoxyalkoxy, hydroxyethyl or phenyl optionally mono- ordi-substituted by halogen and/or (C₁ -C₃)alkyl,

R₆ represents hydrogen, (C₁ -C₄)alkyl, (C₁ -C₄)haloalkyl, phenyloptionally substituted by halogen, nitro and/or (C₁ -C₄)alkyl, or agroup of the general formula ##STR13## R₇ represents (C₁ -C₄)alkyl,phenyl, halophenyl, nitrophenyl or (C₁ -C₄)alkylphenyl,

R₈ represents hydrogen, (C₁ -C₄)alkyl or (C₁ -C₄)alkoxy,

R₉ represents (C₁ -C₄)alkyl, and

p is 0, 1 or 2.

It has further been disclosed in DE-OS (German published specification)2,812,571, corresponding to Japanese Laid-open Patent Application No.54-119,476, that herbicidal activity is possessed by compounds of thegeneral formula ##STR14## wherein X represents fluorine or chlorine,

Y represents hydrogen or chlorine,

R represents hydrogen, methyl or ethyl,

n is 0 or 2,

Z¹ represents hydroxy, (C₁ -C₆)alkoxy whose alkyl moiety is optionallysubstituted by 1 to 3 halogen, (C₁ -C₄)alkoxy-(C₁ -C₄)alkoxy, (C₂-C₄)alkenyloxy, (C₂ -C₄)alkynyloxy, (C₃ -C₆)cycloalkyl whose cycloalkylmoiety is optionally substituted by (C₁ -C₄)alkyl, (C₁-C₄)alkoxycarbonyl-(C₁ -C₄) alkoxy, phenoxy whose phenyl moiety isoptionally substituted by 1 to 3 halogen or (C₁ -C₄)alkyl, benzyloxy,glycidyloxy, (C₁ -C₄)alkylthio, (C₂ -C₄)alkenylthio, phenylthio whosephenyl moiety is optionally substituted by 1 to 3 halogen or (C₁-C₄)alkyl, amino, (C₁ -C₄)-alkylamino, (C₁-C₄)alkoxycarbonylmethylamino, hydroxycarbonylmethylamino, anilino groupwhose phenyl moiety may optionally be substituted by 1 to 3 halogen,pyridin-2-ylamino, an --O-- cation, or halogen.

The present invention now provides, as new compounds, the substitutedphenoxypropionates of the general formula ##STR15## in which R¹ and R²each independently represent a hydrogen atom or a C₁ to C₆ alkyl group,

X represents a hydrogen or halogen atom or a nitro,

C₁ to C₆ alkyl or C₁ to C₆ alkoxy group,

a and n each independently are 1 or 2, and

Ar represents a group of the general formula ##STR16## wherein Yrepresents a trifluoromethyl group, a halogen atom or a nitro, cyano orC₁ to C₆ alkyl group, and

b is 1, 2 or 3.

The invention also provides a process for the preparation of asubstituted phenoxypropionate of the formula (I), in which process

(a) a compound of the general formula ##STR17## in which Ar has themeaning given above, and

M represents a hydrogen atom or an alkali metal atom,

is reacted with a compound of the general formula ##STR18## in which R¹,R², X, a and n have the meanings given above, and

Z¹ represents a halogen atom, or

(b) a compound of the general formula ##STR19## in which Ar has themeaning given above, and

Z² represents a hydroxyl group or a halogen atom, is reacted with acompound of the general formula ##STR20## in which R¹, R², X, a and nhave the meanings given above, or (c) a compound of the general formula

    Ar--Z.sup.1                                                (VI)

in which Ar and Z¹ have the meanings given above, is reacted with acompound of the general formula ##STR21## in which R¹, R², X, M, a and nhave the meanings given above.

Surprisingly the substituted phenoxypropionate compounds of the presentinvention, which have not previously been described in the literature,can be synthesized with ease in high yield, and are novel activecompounds showing selective excellent herbicidal activity againstgramineous weeds without causing substantial phytotoxicity onagricultural crops. It is particularly surprising that the compounds ofthe present invention show excellent properties which are not shown bystructurally similar prior art compounds, in particular that, coupledwith good toleration by useful plants, they show sufficient herbicidalactivity in low amounts, and that they control regeneration of weeds,especially perennial gramineous weeds, over a long period of time due totheir excellent lasting effect.

Preferred compounds according to the present invention, andcorresponding starting materials are those in which

Ar represents a group of formula (Ia) or (Ib),

in which

Y represents a trifluoromethyl group, a fluorine, chlorine, bromine oriodine atom or a nitro, cyano, methyl, ethyl, propyl, isopropyl,

n-, iso-, sec- or tert-butyl group,

b is 1, 2 or 3,

R¹ and R² each independently represent a hydrogen atom or a methyl,ethyl, n-propyl, isopropyl, n-, iso-, sec- or tert-butyl group,

X represents a hydrogen atom, a fluorine, chlorine, bromine or iodineatom, a nitro, methyl, methoxy, ethyl, ethoxy, n-propyl, n-propoxyl,isopropyl, isopropoxy or n-, iso-, sec- or tert-butyl or -butoxy group,and

a and n are each independently 1 or 2.

If 4-(4-trifluoromethylphenoxy)phenol and 2-benzyloxyethyl 2-bromopropionate are used as starting materials, the course of reactionvariant (a) according to the present invention is illustrated by thefollowing equation: ##STR22##

If 2-[4-(3,5-dichloro-2-pyridyloxy)phenoxy]propionyl chloride and1-benzyloxy-2-propanol are used as starting materials, the course ofreaction variant (b) according to the present invention is illustratedby the following equation: ##STR23##

If 4-trifluoromethylphenylchloride and2-(2-fluorobenzyloxy)ethyl-2-(4-hydroxyphenoxy)propionate are used asstarting materials, the course of reaction variant (c) according to thepresent invention is illustrated by the following equation: ##STR24##

Examples of the compounds of the formula (II) used as starting materialsin reaction variant (a) according to the present invention are4-(4-trifluoromethylphenoxy)phenol, 4-(2-trifluoromethylphenoxy)phenol,4-(4-fluorophenoxy)phenol, 4-(2,4-dichlorophenoxy)phenol,4-(2-chloro-4-nitrophenoxy)phenol,4-(2-trifluoromethyl-4-chlorophenoxy)phenol,4-(4-trifluoromethyl-2-chlorophenoxy)phenol,4-(3,5-dichloro-2-pyridyloxy)phenol, 4-(5-nitro-2-pyridyloxy)phenol,4-(4-nitrophenoxy)phenol, 4-(4-bromo-2-chlorophenoxy)phenol,4-(4-trifluoromethyl-2-nitrophenoxy)phenol,4-(2,6-dichloro-4-trifluoromethylphenoxy)phenol,4-(2-cyano-4-trifluoromethylphenoxy)phenol,4-(2-chloro-4-cyanophenoxy)phenol,4-(3-chloro-5-nitro-2-pyridyloxy)phenol,4-(5-trifluoromethyl-2-pyridyloxy)phenol,4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenol,4-(5-bromo-3-chloro-2-pyridyloxy)phenol, and4-(4-chloro-2-methylphenoxy)phenol; as well as the alkali metal (e.g.Li, Na and K) salts thereof.

Examples of the other starting materials of the formula (III) for use inreaction variant (a) are:

2-benzyloxyethyl-2-chloro(or bromo)propionate, 3-benzyloxypropyl2-chloro(or bromo)propionate, 1-methyl-2-benzyloxyethyl 2-chloro(orbromo)propionate, 2-α-methyl-benzyloxyethyl 2-chloro(orbromo)propionate, 2-(2-fluorobenzyloxy)ethyl 2-chloro(orbromo)propionate, 2-(4-fluorobenzyloxy)ethyl 2-chloro(orbromo)propionate, 2-(2-chlorobenzyloxy)ethyl 2-chloro(orbromo)propionate, 2-(4-chlorobenzyloxy)ethyl 2-chloro(orbromo)propionate, 2-(2,4-dichlorobenzyloxy)ethyl 2-chloro(orbromo)propionate, 2-(3,4-dichlorobenzyloxy)ethyl 2-chloro(orbromo)propionate, 2-(2,6-dichlorobenzyloxy)ethyl 2-chloro(orbromo)propionate, 2-(2-methylbenzyloxy)ethyl 2-chloro(orbromo)propionate, 2-(3-nitrobenzyloxy)ethyl 2-chloro(orbromo)propionate, 2-(4-methoxybenzyloxy)ethyl 2-chloro(orbromo)propionate, 2-(4-bromobenzyloxy)ethyl 2-chloro(orbromo)propionate, 1-methyl-2-α-methylbenzyloxyethyl 2-chloro(orbromo)propionate, 2-(3-chlorobenzyloxy)ethyl 2-chloro(orbromo)propionate, 2-(2-bromobenzyloxy)ethyl 2-chloro(orbromo)propionate, 2-(3-fluorobenzyloxy)ethyl 2-chloro(orbromo)propionate, 1-methyl-2-(2-fluorobenzyloxy)ethyl 2-chloro(orbromo)-propionate, 3-(2-fluorobenzyloxy)propyl 2-chloro(orbromo)propionate, 2-(2-nitrobenzyloxy)ethyl 2-chloro(orbromo)propionate, 2-(4-nitrobenzyloxy)ethyl 2-chloro(orbromo)propionate, 2-(4-methylbenzyloxy)ethyl 2-chloro(orbromo)propionate, 2-(2-methoxybenzyloxy)ethyl 2-chloro(orbromo)propionate, and 3-(4-fluorobenzyloxy)propyl 2-chloro(orbromo)propionate.

Reaction variant (a) according to the present invention is preferablycarried out in a presence of a diluent. For this purpose, any inertsolvents may be employed.

Example of such solvents and diluents include water; aliphatic,alicyclic and aromatic hydrocarbons--each of which may optionally bechlorinated (such as hexane, cyclohexane, petroleum ether, ligroin,benzene, toluene, xylene, methylene chloride, chloroform, carbontetrachloride, ethylene chloride, tri-chloroethylene, andchlorobenzene), ethers (such as diethyl ether, methyl ethyl ether,diisopropyl ether, dibutyl ether, propylene oxide, dioxane, andtetrahydrofuran), kenotes (such as acetone, methyl ethyl ketone, methyli-propyl ketone, and methyl isobutyl ketone), nitriles (such asacetonitrile, propionitrile, and acrylonitrile), alcohols (such asmethanol, ethanol, iso-propanol, butanol, and ethylene glycol), esters(such as ethyl acetate and amyl acetate), acid amides (such asdimethylformamide and dimethylacetamide) sulfones and sulfoxides (suchas dimethylsulfoxide and sulfolane) and bases (such as pyridine).

The reaction variant (a) is preferably carried out in the presence of anacid-binding agent. As example of such acid-binding agents, there may bementioned hydroxides, carbonates, bicarbonates and alcoholates of alkalimetals, and tertiary amines such as triethylamine, diethylaniline,pyridine.

Reaction variant (a) can be carried out over a wide range oftemperatures. Generally, it is carried out at a temperature between -20°C. and the boiling point of the reaction mixture, preferably between 0°C. and 100° C.

This reaction variant (a) is preferably carried out under ambientpressure, although it can be effected under elevated or reducedpressure.

Examples of the compounds of the formula (IV) used as starting materialsin reaction variant (b) are:

2-[4-(4-trifluoromethylphenoxy)phenoxy]propionyl chloride,2-[4-(2-trifluoromethylphenoxy)phenoxy]propionyl chloride,2-[4-(4-fluorophenoxy)phenoxy]propionyl chloride,2-[4-(2,4-dichlorophenoxy)phenoxy]propionyl chloride,2-[4-(2-chloro-4-nitrophenoxy)phenoxy]propionyl chloride,2-[4-(2-trifluoromethyl-4-chlorophenoxy)phenoxy]propionyl chloride,2-[4-(3,5-dichloro-2-pyridyloxy)phenoxy]propionyl chloride,2-[4-(4-trifluoromethyl-2-chlorophenoxy)phenoxy]propionyl chloride,2-[4-(5-nitro-2-pyridyloxy)phenoxy]propionyl chloride,2-[4-(4-nitrophenoxy)phenoxy]propionyl chloride,2-[4-(4-bromo-2-chlorophenoxy)phenoxy]propionyl chloride,2-[4-(4-trifluoromethyl-2-nitrophenoxy)phenoxy]propionyl chloride,2-[4-(2,6-dichloro-4-trifluoromethylphenoxy)phenoxy]propionyl chloride,2-[4-(2-cyano-4-trifluoromethylphenoxy)phenoxy]propionyl chloride,2-[4-(2-chloro-4-cyanophenoxy)phenoxy]propionyl chloride,2-[4-(3-chloro-5-nitro-2-pyridyloxy)phenoxy]propionyl chloride,2-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy]-propionyl chloride, 2-[4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenoxy]propionyl chloride,2-[4-(5-bromo-3-chloro-2-pyridyloxy)phenoxy]propionyl chloride, and2-[4-(4-chloro-2-methylphenoxy)phenoxy]propionyl chloride; as well asthe corresponding bromides or free propionic acid derivatives.

Examples of the other starting materials of the formula (V) for use inreaction variant (b) are:

2-benzyloxyethanol, 3-benzyloxypropanol, 1-benzyloxy-2-propanol,2-α-methylbenzyloxyethanol, 2-(2-fluorobenzyloxy)ethanol,2-(4-fluorobenzyloxy)ethanol, 2-(2-chlorobenzyloxy)ethanol,2-(4-chlorobenzyloxy)ethanol, 2-(2,4-dichlorobenzyloxy)ethanol,2-(3,4-dichlorobenzyloxy)ethanol, 2-(2,6-dichlorobenzyloxy)ethanol,2-(2-methylbenzyloxy)ethanol, 2-(3-nitrobenzyloxy)ethanol,2-(4-methoxybenzyloxy)ethanol, 2-(4-bromobenzyloxy)ethanol,1-(α-methylbenzyloxy)-2-propanol, 2-(3-chlorobenzyloxy)ethanol,2-(2-bromobenzyloxy)ethanol, 2-(3-fluorobenzyloxy)ethanol,1-(2-fluorobenzyloxy)-2-propanol, 3-(2-fluorobenzyloxy)propanol,2-(2-nitrobenzyloxy)ethanol, 2-(4-nitrobenzyloxy)ethanol,2-(4-methylbenzyloxy)ethanol, 2-(2-methoxybenzyloxy)ethanol, and3-(4-fluorobenzyloxy)propanol.

In carrying out reaction variant (b) any of the inert solvents ordiluents as described hereinbefore for reaction variant (a) ispreferably used to obtain the end product with high purity in highyield. Likewise reaction variant (b) is preferably carried out in thepresence of an acid-binding agent as described hereinbefore for reactionvariant (a).

Reaction variant (b) can be carried within the same reaction conditionsof temperature and pressure as those mentioned hereinbefore for reactionvariant (a).

Examples of the compounds of the formula (VI) used as starting materialsin reaction variant (c) are: 4-(or 2-)trifluoromethyl chloro (orbromo)benzene, 1-chloro-4-fluorobenzene, 1,2,4-trichlorobenzene,1-bromo-2,4-dichlorobenzene, 3,4-dichloro-nitrobenzene,4-bromo-3-chloro-nitrobenzene, 1,4-dichloro-2-trifluoromethylbenzene,1-bromo-4-chloro-2-trifluoromethylbenzene,1,2-dichloro-4-trifluoromethylbenzene,1-bromo-2-chloro-4-trifluoromethylbenzene, 2,3,5-trichloropyridine,2-bromo-3,5-dichloropyridine, 2-chloro(or bromo)-5-nitropyridine,4-chloro(or bromo)nitrobenzene, 1-bromo-3,4-dichlorobenzene,2-chloro-1,4-dibromobenzene, 2-chloro(orbromo)-5-trifluoromethylnitrobenzene,1,2,3-trichloro-5-trifluoromethylbenzene,1-bromo-2,6-dichloro-4-trifluoromethylbenzene, 2-chloro(orbromo)-5-trifluoromethyl benzonitrile, 3,4-dichlorobenzonitrile,4-bromo-3-chloro benzonitrile, 2,3-dichloro-5-nitropyridine,2-bromo-3-chloro-5-nitropyridine, 2-chloro(orbromo)-5-trifluoromethylpyridine,2,3-dichloro-5-trifluoromethylpyridine,2-bromo-3-chloro-5-trifluoromethylpyridine,5-bromo-2,3-dichloropyridine, 3-chloro-2,5-dibromopyridine,2,5-dichlorotoluene and 2-bromo-5-chlorotoluene.

Example of the other starting materials of the formula (VII) also usedin reaction variant (c) are:

2-benzyloxyethyl 2-(4-hydroxyphenoxy)propionate, 3-benzyloxypropyl2-(4-hydroxyphenoxy)propionate, 1-methyl-2-benzyloxyethyl2-(4-hydroxyphenoxy)propionate, 2-α-methylbenzyloxyethyl2-(4-hydroxyphenoxy)propionate, 2-(2-fluorobenzyloxy)ethyl2-(4-hydroxyphenoxy)propionate, 2-(4-fluorobenzyloxy)ethyl2-(4-hydroxyphenoxy)propionate, 2-(2-chlorobenzyloxy)ethyl2-(4-hydroxyphenoxy)propionate, 2-(4-chlorobenzyloxy)ethyl2-(4-hydroxyphenoxy)propionate, 2-(2,4-dichlorobenzyloxy)ethyl2-(4-hydroxyphenoxy)propionate, 2-(3,4-dichlorobenzyloxy)ethyl2-(4-hydroxyphenoxy)propionate, 2-(2,6-dichlorobenzyloxy)ethyl2-(4-hydroxyphenoxy)propionate, 2-(2-methylbenzyloxy)ethyl2-(4-hydroxyphenoxy)propionate, 2-(3-nitrobenzyloxy)ethyl2-(4-hydroxyphenoxy)propionate, 2-(4-methoxybenzyloxy)ethyl2-(4-hydroxyphenoxy)propionate, 2-(4-bromobenzyloxy)ethyl2-(4-hydroxyphenoxy)propionate, 1-methyl-2-α-methylbenzyloxyethyl2-(4-hydroxyphenoxy)propionate, 2-(3-chlorobenzyloxy)ethyl2-(4-hydroxyphenoxy)propionate, 2-(2-bromobenzyloxy)ethyl2-(4-hydroxyphenoxy)propionate, 2-(3-fluorobenzyloxy)ethyl2-(4-hydroxyphenoxy)propionate, 1-methyl-2-(2-fluorobenzyloxy)ethyl2-(4-hydroxyphenoxy)propionate, 3-(2-fluorobenzyloxy)propyl2-(4-hydroxyphenoxy)propionate, 2-(2-nitrobenzyloxy)ethyl2-(4-hydroxyphenoxy)propionate, 2-(4-nitrobenzyloxy)ethyl2-(4-hydroxyphenoxy)propionate, 2-(2-methoxybenzyloxy)ethyl2-(4-hydroxyphenoxy)propionate, 3-(4-fluorobenzyloxy)propyl2-(4-hydroxyphenoxy)propionate, and 2-(4-methylbenzyloxy)ethyl2-(4-hydroxyphenoxy)propionate; as well as the alkali metal (e.g. Li, Naand K) salts thereof.

In carrying out reaction variant (c) any of the inert solvents ordiluents as described hereinbefore for reaction variant (a) ispreferably used to obtain the end product with high purity in highyield. Likewise reaction variant (c) is preferably carried out in thepresence of an acid-binding agent as described hereinbefore for reactionvariant (a).

Reaction variant (c) can be carried within the same reaction conditionsof temperature and pressure as those mentioned hereinbefore for reactionvariant (a).

The intermediate compound of the formula (III), (which may also be usedas an intermediate in the production of intermediates of the formula(VII)) have not hitherto been disclosed in the literature and form afurther subject of the present invention.

Thus, the present invention further provides a process for theproduction of a compound of the general formula (III), which comprisesreacting a compound of the general formula ##STR25## in which Z¹ and Z²have the meanings given above, with a compound of the general formula##STR26## in which R¹, R², X, a and n have the meanings given above.

Examples of the compounds of the formula (VIII) used as startingmaterials in the production of compounds of formula (III) are:

2-bromopropionic acid and 2-chloropropionic acid; as well as acylchloride and acyl bromide thereof.

Examples of the other starting materials of the formula (IX) also usedin the production of compounds of formula (III) are:

2-benzyloxyethanol, 3-benzyloxypropanol, 1-methyl-2-benzyloxyethanol,2-α-methyl benzyloxyethanol, 2-(2-chlorobenzyloxy)ethanol,2-(3-chlorobenzyloxy)ethanol, 2-(4-chlorobenzyloxy)ethanol,2-(2,4-dichlorobenzyloxy)ethanol, 2-(2,6-dichlorobenzyloxy)ethanol,2-(3,4-dichlorobenzyloxy)ethanol, 2-(2-methylbenzyloxy)ethanol,2-(4-methylbenzyloxy)ethanol, 2-(2-methoxybenzyloxy)ethanol,2-(4-methoxybenzyloxy)ethanol, 2-(2-bromobenzyloxy)ethanol,2-(4-bromobenzyloxy)ethanol, 1-methyl-2-α-methylbenzylethanol,2-(2-fluorobenzyloxy)ethanol, 2-(3-fluorobenzyloxy)ethanol,2-(4-fluorobenzyloxy)ethanol, 2-(2-nitrobenzyloxy)ethanol,2-(3-nitrobenzyloxy)ethanol, 2-(4-nitrobenzyloxy)ethanol,1-methyl-2-(2-fluorobenzyloxy)ethanol, 3-(2-fluorobenzyloxy)propanol,3-(4-fluorobenzyloxy)propanol.

If 2-bromopropionyl bromide and 2-benzyloxyethanol are used as startingmaterials, the course of the reaction for the production of compounds offormula (III) is illustrated by the following equation: ##STR27##

In the process for the production of compounds of formula (III) any ofthe inert solvents or diluents as described hereinbefore for reactionvariant (a) is preferably used to obtain the end products with highpurity in high yield. Likewise this reaction is preferably carried outin the presence of the acid-binding agent as described hereinbefore forreaction variant (a).

The reaction conditions of temperature and pressure are also chosen fromthose mentioned hereinbefore for reaction variant (a).

The starting compounds of formula (VII) are also novel and form afurther subject of the present invention.

The present invention further provides a process for the production of acompound of the formula (VII), which comprises reacting a compound ofthe formula ##STR28## with a compound of the general formula ##STR29##in which R¹, R², X, a, n and Z¹ have the meanings given above.

Example of the compounds of the formula (III) used as starting materialshave already been mentioned as preferred starting materials for reactionvariant (a) and can be prepared as described above.

If hydroquinone and 2-benzyloxyethyl-2-bromopropionate are used asstarting materials, the course of the reaction for the production ofcompounds of formula (VII) is illustrated by the following equation:##STR30##

In the process for the production of compounds of formula (VII) any ofthe inert solvents or diluents as described hereinbefore for reactionvariant (a) is preferably used to obtain the end products with highpurity in high yield. Likewise this reaction is preferably carried outin the presence of the acid-binding agent as described hereinbefore forreaction variant (a).

The reaction conditions of temperature and pressure are also chosen fromthose mentioned hereinbefore for reaction variant (a).

The active compounds of formula (I) according to the present inventionshow excellent selective herbicidal effect when used as soil-treatingagents to be used pre- or post-emergence of gramineous weeds.

Since the active compounds according to the present invention showlittle or no toxicity towards warm-blooded animals and show goodselectivity for agricultural plants, that is, caused no phytotoxicityfor agricultural plants, they can be conveniently used as herbicides forcontrolling weeds.

The active compounds according to the invention influence plant growthand can therefore be used as defoliants, desiccants, agents fordestroying broadleaved plants, germination inhibitors and, especially,as weed-killers. By "weeds" in the broadest sense there are meant plantsgrowing in places where they are not desired.

Whether the compounds according to the invention act as total herbicidesor selective herbicides depends essentially on the amount used.

The active compounds according to the present invention may be used, forexample, to combat the following plants:

dicotyledon weeds of the genera Sinapis, Lepidium, Galium, Stellaria,Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio,Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum,Sesbania, Ambrosia, Cirsium, Carduxs, Sonchus, Rorippa, Rotala,Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis,Papaver, Centaurea and Solanum; and

monocotyledon weeds of the genera Echinochloa, Setaria, Panicum,Digitaria, Phleum, Poa, Festuca, EIeusine, Brachiaria, Lolium, Bromus,Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis,Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea,Dactyloctenium, Agrostis, Alopecurus and Apera.

The active compounds according to the present invention may be used, forexample, as selective herbicides in the following cultures:

dicotyledon cultures of the genera Gossypium, Glycine, Beta, Daucus,Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana,Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita; and

monocotyledon cultures of the genera Oryza, Zea, Triticum, Hordeum,Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus andAllium.

However, the use of the active compounds according to the invention isin no way restricted to these genera but also embraces other plants, inthe same way.

Depending on the concentrations, the compounds can be used for the totalcombating of weeds, for example on industrial terrain and railway tracksand on paths and squares with or without trees. Equally, the compoundscan be employed for combating weeds in perennial cultures, for exampleafforestations, decorative tree plantings, orchards, vineyards, citrusgroves, nut orchards, banana plantations, coffee plantations, teaplantations, rubber plantations, oil palm plantations, cacaoplantations, soft fruit plantings and hopfields, and for the selectivecombating of weeds in annual cultures.

The active compounds according to the present invention may particularlybe used to combat the following plants: Echinochloa crusgalli, Digitariaadscendeno, Eleusine indica, Setaria viridis, Avena fatua, Alopecurusaequalis, Setaria lutescens, Agropyron repens or Agropyron tsukushiense.

In addition, they show excellent herbicidal and regrowth-control effectson, for example, Sorghum halepense or Cynodon dactylon.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, dustingagents, soluble powders, granules, suspension-emulsion concentrates,natural and synthetic materials impregnated with active compound, andvery fine capsules in polymeric substances.

These formulations may be produced in known manner, for example bymixing the active compounds with extenders, that is to say liquid orsolid diluents or carriers, optionally with the use of surface-activeagents, that is to say emulsifying agents and/or dispersing agentsand/or foam-forming agents. In the case of the use of water as anextender, organic solvents can, for example, also be used as auxiliarysolvents.

As liquid diluents or carriers, especially solvents, there are suitablein the main, aromatic hydrocarbons, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic or chlorinated aliphatichydrocarbons, such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane orparaffins, for example mineral oil fractions, alcohols, such as butanolor glycol as well as their ethers and esters, ketones, such as acetone,methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, orstrongly polar solvents, such as dimethylformamide anddimethylsulphoxide, as well as water.

As solid carriers there may be used ground natural minerals, such askaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite ordiatomaceous earth, and ground synthetic minerals, such ashighly-dispersed silicic acid, alumina and silicates. As solid carriersfor granules there may be used crushed and fractionated natural rockssuch as calcite, marble, pumice, sepiolite and dolomite, as well assynthetic granules of inorganic and organic meals, and granules oforganic material such as sawdust, coconut shells, maize cobs and tobaccostalks.

As emulsifying and/or foam-forming agents there may be used non-ionicand anionic emulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well asalbumin hydrolysis products. Dispersing agents include, for example,lignin sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, can be used in theformulations.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs or metal phthalocyaninedyestuffs, and trace nutrients, such as salts of iron, manganese, boron,copper, cobalt, moylbdenum and zinc.

The formulations in general contain from 0.001 to 100 percent by weightof active compound, preferably from 0.005 to 95 percent by weight.

The active compounds according to the invention, as such or in the formof their formulations, can also be used, for combating weeds, asmixtures with known herbicides, finished formulations or tank mixingbeing possible. Mixtures with other known active compounds, such asfungicides, insecticides, acaricides, nematicides, bird repellants,growth factors, plant nutrients and agents which improve soil structure,are also possible.

The active compounds can be used as such, in the form of theirformulations or in the use forms prepared therefrom by further dilution,such as ready-to-use solutions, suspensions, emulsions, powders, pastesand granules. They may be used in the customary manner, for example bywatering, spraying, atomising, scattering or dusting.

The amount of active compound in the ready-to-use preparations can varywidely according to circumstance. However, it is in general from 0.01 to95 percent, preferably from 0.05 to 60 percent by weight.

The compounds can also be used in ultra-low-volume method, wherein thepreparation used can contain up to 100% of the active ingredient.

The active compounds can be applied after emergence of the plants orbefore emergence of the plants, that is to say by the pre-emergencemethod. They can also be incorporated into the soil before sowing.

The amount of active compound used can vary within a substantial range.It depends essentially on the nature of the desired effect. In general,the amounts used are between 0.01 and 2 kg of active compound perhectare, preferably between 0.05 and 1 kg/ha.

The present invention also provides a herbicidal composition containingas active ingredient a compound of the present invention in admixturewith a solid diluent or carrier or in admixture with a liquid diluent orcarrier containing a surface-active agent.

The present invention also provides a method of combating weeds whichcomprises applying to the weeds, or to a habitat thereof, a compound ofthe present invention alone or in the form of a composition containingas active ingredient a compound of the present invention in admixturewith a diluent or carrier.

The present invention further provides crops protected from damage byweeds by being grown in areas in which immediately prior to and/orduring the time of the growing a compound of the present invention wasapplied alone or in admixture with a diluent or carrier.

It will be seen that the usual methods of providing a harvested crop maybe improved by the present invention.

Compositions according to this invention are illustrated in thefollowing Examples.

In these Examples, the compounds according to the present invention areeach identified by the number (given in brackets) of the correspondingpreparative Example. References to "parts" are to be understood asmeaning parts by weight.

EXAMPLE I

Fifteen parts of compound (I), 80 parts of a 1:5 mixture of powdereddiatomaceous earth and powdered clay, 2 parts of sodiumalkylbenzenesulfonate and 3 parts of sodiumalkylnaphthalenesulfonate/formaldehyde condensate were ground and mixedto form a wettable powder. The wettable powder was diluted with waterbefore use.

EXAMPLE II

Thirty parts of compound (11), 55 parts of xylene, 8 parts ofpolyoxyethylene alkylphenyl ether and 7 parts of calciumalkylbenzenesulfonate were mixed with stirring to form an emulsifiableconcentrate. The emulsifiable concentrate was diluted with water beforeuse.

EXAMPLE III

Two parts of compound (12) and 98 parts of powdered clay were pulverizedand mixed to form a dusting agent.

EXAMPLE IV

1.5 parts of compound (13), 0.5 part of isopropyl hydrogen phosphate(PAP) and 98 parts of powdered clay were ground and mixed to form adusting agent.

EXAMPLE V

25 parts of water were added to, and thoroughly mixed with, a mixture of10 parts of compound (14), 30 parts of bentonite (montmorillonite), 58parts of talc and 2 parts of lignin sulfonate. The resultant mixture wasformed into granules having a size of 10 to 40 mesh by means of anextrusion-type granulator, and dried at 40° to 50° C. to form granules.

EXAMPLE VI

A rotary mixer was charged with 95 parts of clay mineral particleshaving a particle size distribution in the range of 0.2 to 2 mm, and,while rotating the mixer, 5 parts of compound (2) dissolved in anorganic solvent were sprayed uniformly onto the clay mineral particles.The particles were then dried at 40° to 50° C. to form granules.

The herbicidal activity of the compounds of the formula (I) isillustrated by the following biotest Examples.

In these Examples, the compounds according to the present invention areeach identified by the number (given in brackets) of the correspondingpreparative Example.

The known comparison compound is identified as follows: ##STR31## (Theyare described in Japanese Laid-open Patent Application No. 51-106,735).##STR32## (A compound described in Japanese Laid-open Patent ApplicationNo. 52-131,545), ##STR33## (A compound described in Japanese Laid-openPatent Application No. 52-144,637). ##STR34## (A compound described inJapanese Laid-open Patent Application No. 54-119,476).

EXAMPLE A Pre-emergence treatment tests for weeds and crops in uplandfields

Preparation of active compound:

Carrier: 5 parts by weight of acetone

Emulsifier: 1 part by weight of benzyloxy polyglycol ether

A preparation of the active compound was obtained as an emulsifiableconcentrate by mixing 1 part by weight of the active compound with theaforesaid amounts of the carrier and the emulsifier. A predeterminedamount of the preparation was obtained by dilution with water. Testingmethod:

Field soils placed in 1,000 cm² pots were respectively seeded withArachis, Pisum, Gossypium and Glycine in a greenhouse, and covered witha soil mixed with seeds of Agropyron repens, Echinochloa crus-galli andSetaria lutescens in a depth of 1 cm. One day after the seeding, 10 mlof the above-prepared solutions respectively containing 500 ppm, 200ppm, 100 ppm, and 50 ppm active ingredient were uniformly applied to thesoil surface layer.

4 weeks after the treatment, the herbicidal effect and degree ofphytotoxicity were evaluated on a scale of from 0 to 10 in accordancewith the following standards.

The herbicidal effect was evaluated as follows in comparison with anuntreated control.

    ______________________________________    Rating      Weed-kill ratio based on the control    ______________________________________    10:         100% (withered)    9:          at least 90% but less than 100%    8:          at least 80% but less than 90%    7:          at least 70% but less than 80%    6:          at least 60% but less than 70%    5:          at least 50% but less than 60%    4:          at least 40% but less than 50%    3:          at least 30% but less than 40%    2:          at least 20% but less than 30%    1:          at least 10% but less than 20%    0:          less than 10% (not effective)    ______________________________________

The phytotoxicity towards the crops was evaluated as follows incomparison with the untreated control.

    ______________________________________    Rating  Phytotoxicity rate in comparison with the control    ______________________________________    10:     at least 90% (fatal damage)    9:      at least 80% but less than 90%    8:      at least 70% but less than 80%    7:      at least 60% but less than 70%    6:      at least 50% but less than 60%    5:      at least 40% but less than 50%    4:      at least 30% but less than 40%    3:      at least 20% but less than 30%    2:      at least 10% but less than 20%    1:      more than 0% but less than 10%    0:      0% (no phytotoxicity)    ______________________________________

The test results are shown in Table 1 in which the symbols a to grepresent the following weeds and crops:

a: Agropyron repens

b: Echinochloa crus-galli

c: Setaria lutescens

d: Arachis

e: Pisum

f: Gossypium

g: Glycine

                  TABLE 1    ______________________________________            Amount of            Effective Herbicidal Effect                                   Phytotoxicity    Compound            Ingredient                      Weed         Crop    No.     kg/ha     a      b    c    d   e    f   g    ______________________________________    1       0.5       10     10   10   0   0    0   0            0.2       10     10   10   0   0    0   0            0.1       8      9    10   0   0    0   0            0.05      6      7    9    0   0    0   0    3       0.5       10     10   10   0   0    0   0            0.2       10     10   10   0   0    0   0            0.1       8      9    10   0   0    0   0            0.05      6      7    9    0   0    0   0    4       0.5       10     10   10   0   0    0   0            0.2       10     10   10   0   0    0   0            0.1       8      9    9    0   0    0   0            0.05      6      7    8    0   0    0   0    36      0.5       10     10   10   0   0    0   0            0.2       10     9    10   0   0    0   0            0.1       8      8    9    0   0    0   0            0.05      6      7    8    0   0    0   0    37      0.5       10     10   10   0   0    0   0            0.2       10     10   10   0   0    0   0            0.1       8      9    10   0   0    0   0            0.05      7      8    9    0   0    0   0    38      0.5       10     10   10   0   0    0   0            0.2       10     10   10   0   0    0   0            0.1       8      9    10   0   0    0   0            0.05      7      8    10   0   0    0   0    39      0.5       10     10   10   0   0    0   0            0.2       10     10   10   0   0    0   0            0.1       9      9    10   0   0    0   0            0.05      8      8    9    0   0    0   0    29      0.5       10     10   10   0   0    0   0            0.2       10     10   10   0   0    0   0            0.1       10     10   10   0   0    0   0            0.05      9      10   10   0   0    0   0    43      0.5       10     10   10   0   0    0   0            0.2       10     10   10   0   0    0   0            0.1       9      9    10   0   0    0   0            0.05      8      7    9    0   0    0   0    14      0.5       10     10   10   0   0    0   0            0.2       10     10   10   0   0    0   0            0.1       8      8    9    0   0    0   0            0.05      6      6    8    0   0    0   0    57      0.5       10     10   10   0   0    0   0            0.2       10     10   10   0   0    0   0            0.1       8      8    9    0   0    0   0            0.05      6      6    8    0   0    0   0    62      0.5       10     10   10   0   0    0   0            0.2       10     10   10   0   0    0   0            0.1       10     10   10   0   0    0   0            0.05      9      9    9    0   0    0   0    63      0.5       10     10   10   0   0    0   0            0.2       10     10   10   0   0    0   0            0.1       9      9    9    0   0    0   0            0.05      8      8    9    0   0    0   0    64      0.5       10     10   10   0   0    0   0            0.2       10     10   10   0   0    0   0            0.1       9      9    9    0   0    0   0            0.05      8      9    9    0   0    0   0    20      0.5       10     10   10   0   0    0   0            0.2       10     10   10   0   0    0   0            0.1       9      9    9    0   0    0   0            0.05      8      8    9    0   0    0   0    22      0.5       10     10   10   0   0    0   0            0.2       10     10   10   0   0    0   0            0.1       9      9    9    0   0    0   0            0.05      8      8    9    0   0    0   0    24      0.5       10     10   10   0   0    0   0            0.2       10     10   10   0   0    0   0            0.1       9      9    9    0   0    0   0            0.05      8      8    8    0   0    0   0    71      0.5       10     10   10   0   0    0   0            0.2       9      10   9    0   0    0   0            0.1       8      9    9    0   0    0   0            0.05      7      8    8    0   0    0   0    73      0.5       10     10   10   0   0    0   0            0.2       10     10   10   0   0    0   0            0.1       9      9    9    0   0    0   0            0.05      8      9    9    0   0    0   0    Com-    parative    Compound    A-1     0.5       7      9    9    0   0    0   0            0.2       5      7    8    0   0    0   0            0.1       2      5    6    0   0    0   0            0.05      0      2    4    0   0    0   0    B-1     0.5       9      10   10   0   0    0   0            0.2       7      8    8    0   0    0   0            0.1       3      6    7    0   0    0   0            0.05      0      3    4    0   0    0   0    ______________________________________

EXAMPLE B Foliage-treating tests for weeds and crops in upland fields

Field soils placed in 2,000 cm² pots were respectively seeded withGlycine, Rephanus and Beta, and covered with a soil mixed with seeds ofEchinochloa crus-galli, Digitaria adscendens, Eleusine indica, Setariaviridis, Avena fatua and Alopecurus aequalis in a depth of 1 cm. 10 daysafter seeding (when weeds were on the average in a second leaf stage andwhen Glycine, Rephanus and Beta were in the initial stage of normalleaf-growing period), 20 ml of the solutions prepared as in Test Example1 and respectively containing 500 ppm, 200 ppm, 100 ppm, and 50 ppmactive ingredient were uniformly applied to the leaves of the plants tobe tested.

3 weeks after the treatment, the herbicidal effect and degree ofphytotoxicity were evaluated in the same manner as in Example A.

The test results are shown in Table 2 in which the symbols h to prepresent the following weeds and crops:

h: Echinochloa crus-galli

i: Digitaria adscendens

j: Eleusine indica

k: Setaria viridis

l: Avena fatua

m: Alopecurus aequalis

n: Glycine

o: Rephanus

p: Beta

                  TABLE 2    ______________________________________            Amount of            Effective  Herbicidal Effect                                       Phytotox-    Compound            Ingredient Weed            icity Crop    No.     kg/ha      h     i   j   k   l   m   n   o   p    ______________________________________    1       0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  10  10  10  0   0   0            0.05       10    10  10  10  10  10  0   0   0    2       0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  10  10  10  0   0   0            0.05       10    10  10  10  10  10  0   0   0    3       0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  10  10  10  0   0   0            0.05       10    10  10  10  9   10  0   0   0    4       0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    9   9   9   9   10  0   0   0            0.05       9     9   9   9   8   9   0   0   0    37      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  10  10  10  0   0   0            0.1        10    10  10  10  10  10  0   0   0            0.05       10    10  10  10  10  10  0   0   0    38      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  10  10  10  0   0   0            0.05       10    10  10  10  10  10  0   0   0    39      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  10  10  10  0   0   0            0.05       10    10  10  10  10  10  0   0   0    29      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  10  10  10  0   0   0            0.05       10    10  10  10  10  10  0   0   0    40      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  10  10  10  0   0   0            0.05       10    10  10  10  10  10  0   0   0    41      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  9   9   8   9   0   0   0            0.05       9     9   8   8   7   8   0   0   0    43      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  10  10  10  0   0   0            0.05       10    10  9   9   9   9   0   0   0    47      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  9   9   10  0   0   0            0.05       9     10  9   8   7   9   0   0   0    48      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  9   9   8   10  0   0   0            0.05       9     9   8   8   7   9   0   0   0    49      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  10  10  10  0   0   0            0.05       10    10  10  10  10  10  0   0   0    50      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  10  9   10  0   0   0            0.05       9     10  9   9   8   9   0   0   0    51      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  10  10  10  0   0   0            0.05       10    10  10  10  9   10  0   0   0    54      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  10  10  10  0   0   0            0.05       10    10  9   9   9   9   0   0   0    56      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  9   9   9   10  0   0   0            0.05       9     9   8   8   8   9   0   0   0    57      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    9   9   9   9   10  0   0   0            0.05       9     8   8   9   7   9   0   0   0    58      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  10  10  10  0   0   0            0.05       10    9   10  9   9   9   0   0   0    16      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  10  10  10  0   0   0            0.05       10    10  9   9   9   10  0   0   0    59      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    9   10  9   9   9   0   0   0            0.05       9     7   9   9   8   9   0   0   0    60      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        9     9   9   9   9   10  0   0   0            0.05       9     8   8   8   8   9   0   0   0    62      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    9   10  10  9   9   0   0   0            0.05       9     8   9   9   9   9   0   0   0    17      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    9   10  10  10  10  0   0   0            0.05       9     8   9   9   9   9   0   0   0    63      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    8   10  10  10  9   0   0   0            0.05       10    8   9   9   9   9   0   0   0    64      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    8   10  10  9   9   0   0   0            0.05       9     7   9   9   8   8   0   0   0    66      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    8   10  9   9   9   0   0   0            0.05       9     7   9   9   8   8   0   0   0    67      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  10  9   10  0   0   0            0.05       10    9   9   9   9   9   0   0   0    20      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  10  10  10  0   0   0            0.05       10    9   9   9   9   9   0   0   0    21      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  10  10  10  0   0   0            0.05       10    9   9   9   9   10  0   0   0    69      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  9   10  10  10  0   0   0            0.05       9     9   9   9   9   9   0   0   0    70      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    9   9   10  9   9   0   0   0            0.05       9     9   9   9   9   9   0   0   0    24      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  10  10  10  0   0   0            0.05       10    9   9   9   9   10  0   0   0    25      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  10  10  10  0   0   0            0.05       10    9   9   9   9   10  0   0   0    71      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  10  10  10  0   0   0            0.05       10    9   10  10  9   9   0   0   0    27      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  10  10  10  0   0   0            0.05       10    10  10  10  9   9   0   0   0    72      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  9   10  9   0   0   0            0.05       10    9   9   9   9   9   0   0    23      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  10  10  10  0   0   0            0.05       10    9   9   9   9   9   0   0   0    75      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  10  10  10  0   0   0            0.05       10    9   9   9   9   9   0   0   0    77      0.5        10    10  10  10  10  10  0   0   0            0.2        10    10  10  10  10  10  0   0   0            0.1        10    10  10  10  10  10  0   0   0            0.05       10    9   9   9   9   9   0   0   0    Compara-    tive    Compound    A-2     0.5        10    10  10  10  9   10  0   0   0            0.2        9     10  9   9   7   10  0   0   0            0.1        7     8   6   7   5   8   0   0   0            0.05       5     5   5   6   4   6   0   0   0    C-1     0.5        10    10  9   10  9   10  0   0   0            0.2        10    9   6   9   6   9   0   0   0            0.1        7     5   3   6   3   6   0   0   0            0.05       3     2   1   3   1   3   0   0   0    ______________________________________

EXAMPLE C Herbicidal and regrowth-control tests for Agropyrontsukushiense

Rice fields where Agropyron tsukushiense was gregarious was divided into1 m² sections. 100 ml portions of solutions prepared as in Test Example1 and respectively containing 1,000 ppm, 500 ppm, 200 ppm, and 100 ppmof the active ingredient were applied to the foliage of Agropyrontsukusiense in each section. 20 days after the treatment, the herbicidaleffects were evaluated in the same manner as in Example A. Further, theeffect of controlling regrowth of Agropyron tsukusiense was evaluated 40days and 60 days after the treatment in accordance with the followingstandards.

    ______________________________________                        Regrowth-control ratio    Rating              based on untreated section    ______________________________________    10:                 100% (complete control of                        regrowth)    9:          at least                        90% but less than 100%    8:          at least                        80% but less than 90%    7:          at least                        70% but less than 80%    6:          at least                        60% but less than 70%    5:          at least                        50% but less than 60%    4:          at least                        40% but less than 50%    3:          at least                        30% but less than 40%    2:          at least                        20% but less than 30%    1:          at least                        10% but less than 20%    0:                  less than 10% (no regrowth-                        control effect)    ______________________________________

The test results are shown in Table 3.

                  TABLE 3    ______________________________________                   Herbicidal                             Regrowth-control           Amount of                   Effect    Effect             Effective 20 Days   40 Days 60 Days    Compound Ingredient                       After     After   After    No.      kg/ha     Application                                 Application                                         Application    ______________________________________     1       1.0       10        10      10             0.5       10        10      10             0.2       10        10      10             0.1       9         8       7    29       1.0       10        10      10             0.5       10        10      10             0.2       10        10      10             0.1       9         8       7    57       1.0       10        10      10             0.5       10        10      10             0.2       10        10      9             0.1       10        9       8    20       1.0       10        10      10             0.5       10        10      10             0.2       10        10      10             0.1       9         9       8    21       1.0       10        10      10             0.5       10        10      10             0.2       10        10      10             0.1       9         8       8    24       1.0       10        10      10             0.5       10        10      10             0.2       10        10      10             0.1       9         8       7    73       1.0       10        10      10             0.5       10        10      10             0.2       10        10      9             0.1       9         9       8    76       1.0       10        10      10             0.5       10        10      10             0.2       10        10      10             0.1       9         8       7    Comparative    Compound    B - 1    1.0       10        10      6             0.5       7         6       3             0.2       4         3       0             0.1       1         0       0    D - 1    1.0       10        10      7             0.5       9         7       2             0.2       6         3       0             0.1       3         0       0    ______________________________________

EXAMPLE D Herbicidal and regrowth-control test for Cynodon dactylon

Upland field where Cynodon dactylon was gregarious was divided into 1 m²sections. The active ingredient in the same quantities as in Example Cwas treated to the Cynodon dactylon.

Herbicidal effect was evaluated 20 days after the treatment, andregrowth-control effect was evaluated 40 days and 60 days after thetreatment in accordance with the same manner as in the foregoingExamples A to C.

The test results are shown in Table 4.

                  TABLE 4    ______________________________________                   Herbicidal                             Regrowth-control           Amount of                   Effect    Effect             Effective 20 Days   40 Days 60 Days    Compound Ingredient                       After     After   After    No.      kg/ha     Application                                 Application                                         Application    ______________________________________     1       1.0       10        10      10             0.5       10        10      10             0.2       10        10      10             0.1       8         7       5     2       1.0       10        10      10             0.5       10        10      10             0.2       10        10      8             0.1       10        8       7     4       1.0       10        10      10             0.5       10        10      10             0.2       10        10      9             0.1       9         8       6    37       1.0       10        10      10             0.5       10        10      10             0.2       10        10      8             0.1       9         8       7    20       1.0       10        10      10             0.5       10        10      10             0.2       10        9       8             0.1       9         9       7    21       1.0       10        10      10             0.5       10        10      10             0.2       10        9       8             0.1       9         8       7    74       1.0       10        10      10             0.5       10        10      10             0.2       10        9       8             0.1       9         8       7    78       1.0       10        10      10             0.5       10        10      10             0.2       10        9       8             0.1       9         7       6    Comparative    Compound    B - 1    1.0       10        9       5             0.5       8         5       2             0.2       5         2       0             0.1       4         0       0    D - 1    1.0       10        10      7             0.5       9         7       5             0.2       7         3       0             0.1       5         1       0    ______________________________________

Other compounds of the present invention employed in the foregoingExamples A to D were also confirmed to show excellent herbicidal effectin the same low amount as in the foregoing Examples A to D and to showregeneration-controlling effect on perennial gramineous weeds over along period of time.

The following examples serve to illustrate processes for the productionof compounds according to the present invention.

PREPARATIVE EXAMPLES EXAMPLE 1 ##STR35##

25.4 g of 4-(4-trifluoromethylphenoxy)phenol were added to 150 ml of dryacetonitrile, and 28.7 g of 2-benzyloxyethyl 2-bromopropionate and 14.5g of anhydrous potassium carbonate were added thereto. Then, the mixturewas refluxed for 4 hours, stirring well. After the completion of thereaction, acetonitrile was distilled off under reduced pressure.

Toluene was added to the residue, and the toluene layer was washedsuccessively with 1% strength by weight sodium hydroxide aqueoussolution and water. Upon distilling off toluene under reduced pressure,there was obtained 41 g of colourless, viscous end product,2-benzyloxyethyl 2-(4-[4-trifluoromethylphenoxy)phenoxy]propionate.n_(D) ²⁰ 1.5300

EXAMPLE 2 ##STR36##

30.6 g of 4-(3,5-dichloro-2-pyridyloxy)phenol sodium salt and 30.5 g of2-(4-fluorobenzyloxy)ethyl 2-chloropropionate were added to 100 ml ofdimethylformamide, and the mixture was heated to 70° to 80° C. for 3hours with stirring. After cooling to room temperature, the reactionsolution was poured into 300 ml of water, then extracted with ether. Theether layer was washed successively with 1% strength by weight sodiumhydroxide aqueous solution and water, followed by dehydration. Upondistilling off the ether, there were obtained 38 g of a pale yellow,viscous, oily end product, 2-(4-fluorobenzyloxy)ethyl2-[4-(3,5-dichloro-2-pyridyloxy)phenoxy]propionate. n_(D) ²⁰ 1.5643

EXAMPLE 3 ##STR37##

22.1 g of 2-(2,6-dichlorobenzyloxy)ethanol and 10.1 g of triethylaminewere dissolved in 200 ml of toluene, then cooled to 0° C. To thissolution was dropwise added a solution of 34.5 g of2-[4-(4-trifluoromethylphenoxy)phenoxy]propionyl chloride in 50 ml oftoluene at 0° to 10° C. After the dropwise addition, the reactionmixture was gradually heated and, at 40° C., it was stirred for one hourto complete the reaction. After cooling the reaction solution to roomtemperature, it was washed successively with 1% strength by weightsodium hydroxide aqueous solution and water, then dehydrated. Afterdistilling off toluene under reduced pressure, the resulting colorless,viscous, oily product was allowed to stand for about 1 month to obtain49.2 g of crystalline 2-(2,6-dichlorobenzyloxy)ethyl2-[4-(4-trifluoromethylphenoxy)phenoxy]propionate. m.p. 51° to 53° C.

EXAMPLE 4 ##STR38##

16.6 g of 1-benzyloxy-2-propanol and 10.6 g of triethylamine weredissolved in 200 ml of toluene, then cooled to 0° C. To this solutionwas dropwise added a solution of 34.7 g of2-[4-(3,5-dichloro-2-pyridyloxy)phenoxy]-propionyl chloride in 80 ml oftoluene at 0° to 5° C. with stirring. After the dropwise addition, themixture was gradually heated and, at 40° to 50° C., it was stirred forone hour to complete the reaction. After cooling to room temperature, itwas washed successively with 1% strength by weight sodium hydroxideaqueous solution and water, followed by drying. Upon distilling offtoluene under reduced pressure, there were obtained 43.3 g of paleyellow, viscous, oily 1-methyl-2-benzyloxyethyl2-[4-(3,5-dichloro-2-pyridyloxy)phenoxy]propionate. n_(D) ²⁰ 1.5710

EXAMPLE 5

In the same manner as described in Example 1 or 2 but using startingmaterials given in the following table, there were synthesized thecompounds of the present invention as shown in the table.

    __________________________________________________________________________    Example    No.  Starting Material                        Starting Material                                      Product    __________________________________________________________________________     6   4-(4-Trifluoromethyl-                        1-Methyl-2-(2-fluorobenzy-                                      1-Methyl-2-(2-fluorobenzyloxy)-         phenoxy)phenol loxy)ethyl 2-chloro-                                      ethyl 2-[4-(4-trifluoromethyl-                        propionate    phenoxy]propionate     7   4-(4-Trifluoromethyl-                        3-(2-Flourobenzyloxy)-                                      3-(2-Fluorobenzyloxy)propyl         phenoxy)phenol propyl 2-bromopropionate                                      2-[4-(4-trifluoromethylphenoxy)-                                      phenoxy]propionate     8   4-(4-Trifluoromethyl-                        2-(3-Chlorobenzyloxy)-                                      2-(3-Chlorobenzyloxy)ethyl         phenoxy)phenol sodium salt                        ethyl 2-chloropropionate                                      2-[4-(4-trifluoromethylphenoxy)-                                      phenoxy]propionate     9   4-(4-Trifluoromethyl-                        2-(2-Bromobenzyloxy)ethyl                                      2-(2-Bromobenzyloxy)ethyl         phenoxy)phenol sodium salt                        2-chloropropionate                                      2-[4-(4-trifluoromethylphenoxy)-                                      phenoxy]propionate    10   4-(4-Trifluoromethyl-                        2-(4-Methylbenzyloxy)-                                      2-(4-Methylbenzyloxy)ethyl 2-         phenoxy)phenol sodium salt                        ethyl 2-bromopropionate                                      [4-(4-trifluoromethylphenoxy)-                                      phenoxy]propionate    11   4-(4-Trifluoromethylphenoxy)-                        2-(2-Methoxybenzyloxy)-                                      2-(2-Methoxybenzyloxy)ethyl 2-         phenol sodium salt                        ethyl 2-bromopropionate                                      [4-(4-trifluoromethylphenoxy)-                                      phenoxy]propionate    12   4-(4-Trifluoromethyl-2-                        2-Benzyloxyethyl                                      2-Benzyloxyethyl 2-[4-(4-tri-         chlorophenoxy)phenol                        2-chloropropionate                                      fluoromethyl-2-chlorophenoxy)-         sodium salt                  phenoxy]propionate    13   4-(4-Bromo-2-chlorophenoxy)-                        2-Benzyloxyethyl                                      2-Benzyloxyethyl         phenol sodium salt                        2-chloropropionate                                      2-[4-(4-bromo-2-chlorophenoxy)-                                      phenoxy]propionate    14   4-(2-Chloro-4-cyano-                        2-Benzyloxyethyl                                      2-Benzyloxyethyl         phenoxy)phenol sodium salt                        2-chloropropionate                                      2-[4-(2-chloro-4-cyanophenoxy)-                                      phenoxy]propionate    15   4-(2,6-Dichloro-4-trifluoro-                        2-Benzyloxyethyl                                      2-Benzyloxyethyl         methylphenoxy)phenol sodium                        2-chloropropionate                                      2-[4-(2,6-dichloro-4-trifluoro-         salt                         methylphenoxy)phenoxy]propionate    __________________________________________________________________________    Example    No.  Starting Material                        Starting Material                                      Product/Physical Constant    __________________________________________________________________________    16   4-(3,5-Dichloro-2-                        1-Methyl-2-α-methyl-                                      1-Methyl-2-α-methylbenzyloxy-         pyridyloxy)phenol sodium                        benzyloxyethyl                                      ethyl 2-[4-(3,5-dichloro-2-         salt           2-chloropropionate                                      pyridyloxy)phenoxy]propionate    17   4-(3,5-Dichloro-2-                        3-(4-Fluorobenzyloxy)-                                      3-(4-Fluorobenzyloxy)propyl         pyridyloxy)phenol sodium                        propyl 2-bromopropionate                                      2-[4-(3,5-dichloro-2-pyridyloxy)-         salt                         phenoxy]propionate    18   4-(3,5-Dichloro-2-pyridyl-                        2-(3-Chlorobenzyloxy)-                                      2-(3-Chlorobenzyloxy)ethyl         oxy)phenol sodium salt                        ethyl 2-chloropropionate                                      2-[4-(3,5-dichloro-2-pyridyloxy)-                                      phenoxy]propionate    19   4-(3,5-Dichloro-2-pyridyl-                        2-(4-Methylbenzyloxy)-                                      2-(4-Methylbenzyloxy)ethyl         oxy)phenol sodium salt                        ethyl 2-chloropropionate                                      2-[4-(3,5-dichloro-2-pyridyloxy)-                                      phenoxy]propionate    20   2-Benzyloxyethanol                        2-[4-(5-Trifluoromethyl-                                      2-Benzyloxyethyl 2-[4-(5-tri-                        2-pyridyloxy)phenoxy]-                                      fluoromethyl-2-pyridyloxy)-                        propionyl chloride                                      phenoxy]propionate/m.p. 44-47°                                      C.    21   2-(2-Fluorobenzyloxy)-                        2-[4-(5-Trifluoromethyl-                                      2-(2-Fluorobenzyloxy)ethyl 2-[4-         ethanol        2-pyridyloxy)phenoxy]-                                      (5-trifluoromethyl-2-pyridyloxy)-                        propionyl chloride                                      phenoxy]propionate/m.p. 46-48.5°                                      C.    22   2-(4-Chlorobenzyloxy)-                        2-[4-(5-Trifluoromethyl-                                      2-(4-Chlorobenzyloxy)ethyl 2-[4-         ethanol        2-pyridyloxy)phenoxy-                                      (5-trifluoromethyl-2-pyridyloxy)-                        propionyl chloride                                      phenoxy]propionate/n.sub.D.sup.20                                      1.5350    23   2-(4-Methoxybenzyloxy)-                        2-[4-(5-trifluoromethyl-                                      2-(4-Methoxybenzyloxy)ethyl 2-[4-         ethanol        2-pyridyloxy)phenoxy]-                                      (5-trifluoromethyl-2-pyridyloxy)-                        propionyl bromide                                      phenoxy]propionate/n.sub.D.sup.20                                      1.5335    24   1-Benzyloxy-2-propanol                        2-[4-(5-Trifluoromethyl-2-                                      1-Methyl-2-benzyloxethyl 2-[4-                        pyridyloxy)phenoxy]-                                      (5-trifluoromethyl-2-pyridyloxy)-                        propionyl bromide                                      phenoxy]propionate/n.sub.D.sup.20                                      1.5224    25   3-Benzyloxypropanol                        2-[4-(5-Trifluoromethyl-                                      3-Benzyloxypropyl 2-[4-(5-tri-                        2-pyridyloxy)phenoxy]-                                      fluoromethyl-2-pyridyloxy)phenoxy]-                        propionyl chloride                                      propionate/n.sub.D.sup.20    __________________________________________________________________________                                      1.5245    Example    No.  Starting Material                        Starting Material                                      Product    __________________________________________________________________________    26   2-Benzyloxyethanol                        2-[4-(3-Chloro-5-nitro-2-                                      2-Benzyloxyethyl 2-[4-(3-                        pyridyloxy)phenoxy]-                                      chloro-5-nitro-2-pyridyloxy)-                        propionyl bromide                                      phenoxy]propionate    27     "            2-[4-(3-Chloro-5-triflu-                                      2-Benzyloxyethyl                        oromethyl-2-pyridyloxy)-                                      2-[4-(3-chloro-5-trifluoromethyl-                        phenoxy]propionyl chloride                                      2-pyridyloxy)phenoxy]propionate    28   2-(2-Methoxybenzyloxy)-                        2-[4-(3,5-Dichloro-2-                                      2-(2-Methoxybenzyloxy)ethyl         ethanol        pyridyloxy)phenoxy]-                                      2-[4-(3,5-dichloro-2-pyridyloxy)-                        propionyl chloride                                      phenoxy]propionate    __________________________________________________________________________

EXAMPLE 29 ##STR39##

33.4 g of 2-(2-fluorobenzyloxy)ethyl-2-(4-hydroxyphenoxy)propionate weredissolved in 120 ml of dimethylformamide, 15.2 g of potassium carbonatewere added thereto, then the mixture was heated at 95° C. for one hourwith stirring. 27.1 g of 4-trifluoromethyl chlorobenzene were added tothe solution which was then heated to 95° to 100° C. for five hours.After cooling the reaction solution to room temperature, it was pouredinto ice-water, then extracted with toluene. The toluene layer waswashed successively with 1% strength by weight sodium hydroxide solutionand water, and was dried and filtered. The toluene was distilled offunder reduced pressure, and further volatile by-products were removed at100° C./0.1 mmHg. The end product of2-(2-fluorobenzyloxy)ethyl-2-[4-(4-trifluoromethylphenoxy)phenoxy]propionatewas obtained in a yield of 20.7 g. (n_(D) ²⁰ 1.5235)

EXAMPLE 30 ##STR40##

31.6 g of 2-benzyloxyethyl-2-(4-hydroxyphenoxy)propionate were dissolvedin 100 ml of dimethylsulfoxide, 15.2 g of potassium carbonate were addedthereto, then the mixture was heated at 90° C. for one hour withstirring. 20.0 g of 2-chloro-5-trifluoromethylpyridine were addeddropwise to this solution which was then maintained at 90° C. for afurther two hours. After cooling the reaction solution to roomtemperature, it was poured into ice-water, then extracted with ether.The ether layer was dried and filtrated, and the ether was distillatedoff. The end product of2-benzyloxyethyl-2-[4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy]propionate(a compound also produced in Example 20) was obtained in a yield of 41.0g (m.p. 44°-47° C.).

EXAMPLES 31 TO 78

Compounds of the present invention shown in following Table 5 wereobtained in substantially the same manner as in the foregoing Examples 1to 30 (or, in the case of Example 40, as in foregoing Examples 1 to 28).

                                      TABLE 5    __________________________________________________________________________     ##STR41##    Example                       Physical    No.  Ar        R.sup.1                       R.sup.2                           n X.sub.a                                  constant    __________________________________________________________________________    31          ##STR42##                   H   H   1 H    n.sub.D.sup.20 1.5322    32          ##STR43##                   H   H   1 H    n.sub.D.sup.20 1.5518    33          ##STR44##                   H   H   1 H    n.sub.D.sup.20 1.5696    34          ##STR45##                   H   H   1 H    n.sub.D.sup.20 1.5805    35          ##STR46##                   H   H   1 H    n.sub.D.sup.20 1.5397    36          ##STR47##                   H   H   1 H    n.sub.D.sup.20 1.5450    37          ##STR48##                   H   H   2 H    n.sub.D.sup.20 1.5268    38          ##STR49##                   CH.sub.3                       H   1 H    n.sub.D.sup.20 1.5260    39          ##STR50##                   H   CH.sub.3                           1 H    n.sub.D.sup.20 1.5266    40          ##STR51##                   H   H   1 4-F  n.sub.D.sup.20 1.5214    41          ##STR52##                   H   H   1 2-Cl n.sub.D.sup.20 1.5360    42          ##STR53##                   H   H   1 2-Cl n.sub.D.sup.20 1.5550    43          ##STR54##                   H   H   1 4-Cl n.sub.D.sup.20 1.5360    44          ##STR55##                   H   H   1 4-Cl n.sub.D.sup.20 1.5380    45          ##STR56##                   H   H   1 4-Cl n.sub.D.sup.20 1.5450    46          ##STR57##                   H   H   1 4-Cl n.sub.D.sup.20 1.5559    47          ##STR58##                   H   H   1 2,4-Cl.sub.2                                  n.sub.D.sup.20 1.5422    48          ##STR59##                   H   H   1 3,4-Cl.sub.2                                  n.sub.D.sup.20 1.5428    49          ##STR60##                   H   H   1 2-CH.sub.3                                  n.sub.D.sup.20 1.5305    50          ##STR61##                   H   H   1 3-NO.sub.2                                  n.sub.D.sup.20 1.5436    51          ##STR62##                   H   H   1 4-OCH.sub.3                                  n.sub.D.sup.20 1.5343    52          ##STR63##                   H   H   2 H    n.sub.D.sup.20 1.5440    53          ##STR64##                   H   H   1 4-Cl n.sub.D.sup.20 1.5875    54          ##STR65##                   H   H   1 4-Br n.sub.D.sup.20 1.5450    55          ##STR66##                   H   H   1 H    n.sub.D.sup.20 1.5650    56          ##STR67##                   H   H   1 2-Cl n.sub.D.sup.20 1.5718    57          ##STR68##                   H   H   1 H    m.p. 59-61° C.    58          ##STR69##                   H   CH.sub.3                           1 H    n.sub.D.sup.20 1.5715    59          ##STR70##                   H   H   2 H    n.sub.D.sup.20 1.5721    60          ##STR71##                   H   H   1 H    oil    61          ##STR72##                   H   H   1 3-NO.sub.2                                  oil    62          ##STR73##                   H   H   1 2-F  m.p. 54-57° C.    63          ##STR74##                   H   H   1 2-Cl m.p. 64-66° C.    64          ##STR75##                   H   H   1 4-Cl n.sub.D.sup.20 1.5803    65          ##STR76##                   H   H   1 4-Cl oil    66          ##STR77##                   H   H   1 3-NO.sub.2                                  n.sub.D.sup.20 1.5845    67          ##STR78##                   H   H   1 2-CH.sub.3                                  m.p. 83-85° C.    68          ##STR79##                   H   H   1 2,4-Cl.sub.2                                  oil    69          ##STR80##                   H   H   1 3,4-Cl.sub.2                                  n.sub.D.sup.20 1.5900    70          ##STR81##                   H   H   1 2,6-Cl.sub.2                                  n.sub.D.sup.20 1.5915    71          ##STR82##                   H   H   1 4-OCH.sub.3                                  n.sub.D.sup.20 1.5735    72          ##STR83##                   H   H   1 4-Br n.sub.D.sup.20 1.5870    73          ##STR84##                   H   CH.sub.3                           1 H    n.sub.D.sup.20 1.5254    74          ##STR85##                   H   H   1 2-CH.sub.3                                  n.sub.D.sup.20 1.5273    75          ##STR86##                   H   H   1 2-Cl n.sub.D.sup.20 1.5349    76          ##STR87##                   H   H   1 4-Br n.sub.D.sup.20 1.5440    77          ##STR88##                   H   H   1 3-NO.sub.2                                  n.sub.D.sup.20 1.5428    78          ##STR89##                   H   H   1 2,4-Cl.sub.2                                  n.sub.D.sup.20 1.5424    __________________________________________________________________________

Processes for the preparation of the novel intermediate compounds offormulae (III) and (VII) according to the present invention areillustrated by the following Examples.

EXAMPLE 79 ##STR90## (a compound of formula (III).

15.2 g of 2-benzyloxyethanol and 10.6 g of triethylamine were dissolvedin 150 ml of toluene, and the solution was cooled to -5° C. A solutionof 21.6 g of 2-bromopropionylbromide in 30 ml of toluene was addeddropwise thereto at -5° to 0° C. with stirring. The reaction mixture wasfurther maintained at room temperature for two hours. The mixtue wasthen washed successively with 1% strength by weight sodium hydroxidesolution and water, and the toluene solution was then dried andfiltered. The toluene was distilled off under reduced pressure, and theend product of 2-benzyloxyethyl-2-bromopropionate was obtained in ayield of 26.7 g (n_(D) ²⁰.5 1.5182)

The intermediate compounds of the general formula (III) of thisinvention shown in Table 6 were produced in a manner similar to thatdescribed above:

                  TABLE 6    ______________________________________     ##STR91##                    (III)    Z.sup.1        R.sup.1  R.sup.2                        n     X.sub.a                                     Physical constant    ______________________________________    Br  H        H      1     2-F    n.sub.D.sup.20 1.5038    Cl  H        H      1     4-F    n.sub.D.sup.20 1.5004    Br  H        H      1     4-F    n.sub.D.sup.20 1.5040    Br  H        H      1     2-Cl   n.sub.D.sup.20.5 1.5302    Br  H        H      1     4-Cl   n.sub.D.sup.20 1.5289    Cl  H        H      1     4-Br   n.sub.D.sup.20.5 1.5321    Br  H        H      1     4-Br   n.sub.D.sup.20.5 1.5434    Br  H        H      1     2-CH.sub.3                                     n.sub.D.sup.20 1.5186    Br  H        H      1     2-OCH.sub.3                                     n.sub.D.sup.20.5 1.5260    Br  H        H      1     3-NO.sub.2                                     n.sub.D.sup.20 1.5394    Br  H        H      1     2,4-Cl.sub.2                                     n.sub.D.sup.20 1.5395    Br  H        H      1     3,4-Cl.sub.2                                     n.sub.D.sup.20 1.5409    Cl  H        H      1     2,6-Cl.sub.2                                     n.sub.D.sup.20 1.5412    Br  CH.sub.3 H      1     H      n.sub.D.sup.20.5 1.5100    Br  H        CH.sub.3                        1     H      n.sub.D.sup.20.5 1.5116    Br  H        H      2     H      n.sub.D.sup.20.5 1.5130    Br  H        H      1     4-OCH.sub.3                                     n.sub.D.sup.20.5 1.5250    ______________________________________

EXAMPLE 80 ##STR92## (a compound of formula (VII)).

12.1 g of hydroquinone were dissolved in 60 ml of dry dimethylformamide,31.7 g of potassium carbonate were added thereto in a slow stream ofnitrogen, and then the mixture was heated to 90° to 95° C. for one hourwith stirring. The mixture was cooled to 60° C., and to it were addeddropwise 28.7 g of 2-benzyloxyethyl-2-bromopropionate. The reactionmixture was heated at 90° C. for two hours. After cooling the reactionsolution to room temperature, it was poured into ice-water and adjustedto pH7, then extracted with 100 ml of toluene. The toluene layer wasdried and filtered, and then toluene was removed under reduced pressure.The colorless oily product of2-benzyloxyethyl-2-(4-hydroxyphenoxy)propionate was obtained in a yieldof 24.6 g. (n_(D) ²¹.5 1.5390)

The intermediates compound of the general formula (VII) of thisinvention shown in Table 7 were produced in a manner similar to thatdescribed above:

                  TABLE 7    ______________________________________     ##STR93##                   (VII)    M     R.sup.1 R.sup.2                         n     X.sub.a Physical constant    ______________________________________    H     H       H      1     2-F     n.sub.D.sup. 21.5 1.5260    H     H       H      1     4-Cl    n.sub.D.sup. 21.5 1.5473    H     H       H      1     3,4-Cl.sub.2                                       n.sub.D.sup. 21.5 1.5570    H     CH.sub.3                  H      1     H       n.sub.D.sup. 20.5 1.5321    H     H       CH.sub.3                         1     H       n.sub.D.sup. 20.5 1.5336    H     H       H      2     H       n.sub.D.sup. 21.5 1.5344    H     H       H      1     4-OCH.sub.3                                       n.sub.D.sup. 20.5 1.5422    ______________________________________

It will be understood that the specification and examples areillustrative but not limitative of the present invention and that otherembodiments within the spirit and scope of the invention will suggestthemselves to those skilled in the art.

What is claimed is:
 1. A substituted phenoxypropionate of the formula##STR94## in which R¹ and R² each independently is a hydrogen atom or aC₁ to C₆ alkyl group,X is a hydrogen or halogen atom, a nitro, C₁ to C₆alkyl or C₁ to C₆ alkoxy group, a and n each independently is 1 or 2, Yis a trifluoromethyl group, a halogen atom or a nitro, cyano or C₁ to C₆alkyl group, and b is 1, 2 or
 3. 2. Compound as claimed in claim 1wherein R¹ is hydrogen.
 3. Compound as claimed in claim 1 wherein R¹ isa C₁ to C₆ alkyl group.
 4. Compound as claimed in claim 1 wherein R² ishydrogen.
 5. Compound as claimed in claim 1 wherein R² is a C₁ to C₆alkyl group.
 6. Compound as claimed in claim 1 wherein X is hydrogen,halogen, nitro, C₁ to C₄ alkyl or C₁ to C₄ alkoxy.
 7. Compound asclaimed in claim 1 wherein a is 1 or
 2. 8. Compound as claimed in claim1 wherein n is 1 or
 2. 9. Compound as claimed in claim 1, wherein R¹ andR² each independently is hydrogen, methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl or tert-butyl, X is a hydrogen atom, a fluorine,chlorine, bromine or iodine atom, a nitro, methyl, methoxy, ethyl,ethoxy, n-propyl, n-propoxyl, isopropyl, isopropoxy or n-, iso-, sec- ortert-butyl or -butoxy group, a and n each independently is 1 or 2, Y isa trifluoromethyl group, a fluorine, chlorine, bromine or iodine atom ora nitro, cyano, methyl, ethyl, propyl, isopropyl, n-, iso-, sec- ortert-butyl group and b is 1, 2 or
 3. 10. Compound as claimed in claim 1,designated 2-(4-chlorobenzyloxy)-ethyl2-(4-(4-trifluoromethylphenoxy)phenoxy)-propionate of the formula##STR95##
 11. Compound as claimed in claim 1, designated2-benzyloxyethyl 2-(4-(4-trifluoromethylphenoxy)-phenoxy)propionate ofthe formula ##STR96##
 12. Compound as claimed in claim 1, designated3-benzyloxypropyl 2-(4(4-trifluoromethylphenoxy)-phenoxy)propionate ofthe formula ##STR97##
 13. Compound as claimed in claim 1, designated2-α-methylbenzyloxyethyl2-(4(4-trifluoromethyl-phenoxy)phenoxy)-propionate of the formula##STR98##
 14. Compound as claimed in claim 1, designated2-(2-fluorobenzyloxy)-ethyl2-(4-(4-trifluoromethyl-phenoxy)phenoxy)-propionate of the formula##STR99##
 15. Compound as claimed in claim 1, designated1-methyl-2-benzyloxyethyl2-(4-(4-trifluoromethyl-phenoxy)phenoxy)-propionate of the formula##STR100##
 16. A herbicidal composition comprising an agriculturallyacceptable carrier and, in herbicidally effective amount, a substitutedphenoxypropionate as claimed in claim
 1. 17. A herbicidal composition asclaimed in claim 30 containing from 0.01 to 95% of the active compound,by weight.
 18. A method of combating weeds which comprises applying tothe weeds, or their habitat, a herbicidally effective amount of asubstituted phenoxypropionate according to claim
 1. 19. A method asclaimed in claim 18, wherein said compound is applied at a dosage of0.01 to 2 kg per hectare.
 20. A method as claimed in claim 19, whereinsaid compound is applied at a dosage of 0.05 to 1 kg per hectare.
 21. Amethod as claimed in claim 18, wherein said substitutedphenoxypropionate compound is selected from2-(4-chlorobenzyloxy)ethyl2-(4-(4-trifluoromethylphenoxy)phenoxy)propionate, 2-benzyloxyethyl2-(4-(4-trifluoromethylphenoxy)phenoxy)-propionate, 3-benzyloxypropyl2-(4-(4-trifluoromethylphenoxy)phenoxy)-propionate,2-α-methylbenzyloxyethyl2-(4-(4-trifluoromethylphenoxy)phenoxy)-propionate,2-(2-fluorobenzyloxy)-ethyl2-(4-(4-trifluoromethylphenoxy)phenoxy)-propionate, and1-methyl-2-benzyloxyethyl2-(4-(4-trifluoromethylphenoxy)phenoxy)-propionate.
 22. A substituted2-halogenopropionate of the formula ##STR101## in which R¹ and R² eachindependently is a hydrogen atom or a C₁ to C₆ alkyl group,X is ahydrogen or halogen atom or a nitro, C₁ to C₆ alkyl or C₁ to C₆ alkoxygroup, a and n each independently is 1 or 2, and Z¹ is a halogen atom ora 4-hydroxyphenoxy group.